Alkoxylation process catalyzed by lanthanum silicates and metasilicates

ABSTRACT

Alkylene oxide adducts of organic compounds having active hydrogen atoms are prepared by a process which comprises contacting and reacting an alkylene oxide reactant comprising one or more vicinal alkylene oxides with an active hydrogen containing reactant comprising one or more compounds having active hydrogen atoms in the presence of a catalytically effective amount of one or more lanthanum compounds comprising silicate, metasilicate and mixtures thereof. The product alkoxylates are known to be useful, for instance, as nonionic surfactants, wetting and emulsifying agents, solvents, and chemical intermediates.

FIELD OF THE INVENTION

This invention relates to an alkoxylation process in which alkyleneoxides are reacted with compounds having active hydrogen atoms in thepresence of catalysts comprising one or more lanthanum silicates and/ormetasilicates. In particularly preferred embodiments, the inventionrelates to processes for the preparation of alkoxylate products usefulas nonionic surfactants.

BACKGROUND OF THE INVENTION

A large variety of products useful, for instance, as nonionicsurfactants, wetting and emulsifying agents, solvents, and chemicalintermediates, are prepared by the addition reaction (alkoxylationreaction) of alkylene oxides (epoxides) with organic compounds havingone or more active hydrogen atoms. For example, particular mention maybe made of the alkanol ethoxylates and alkyl-substituted phenolethoxylates prepared by the reaction of ethylene oxide with aliphaticalcohols or substituted phenols of about 6 to 30 carbon atoms. Suchethoxylates, and to a lesser extent corresponding propoxylates andcompounds containing mixed oxyethylene and oxypropylene groups, arewidely employed as nonionic detergent components of commercial cleaningformulations for use in industry and in the home. As another example,the addition reaction of propylene oxide with polyols providesintermediates for the preparation of polyurethane products.

An illustration of the preparation of an alkanol ethoxylate (representedby formula III below) by addition of a number (n) of ethylene oxidemolecules (formula II) to a single alkanol molecule (formula I) ispresented by the equation ##STR1##

The addition of alkylene oxides to alcohols and other active hydrogencontaining compounds is known to be desirably promoted by a catalystwhich is in conventional practice either basic or acidic in character.Recognized in the art as suitable basic catalysts are the basiccompounds of the alkali metals of Group I of the Periodic Table, e.g.,sodium, potassium, rubidium, and cesium, and the basic salts of certainof the alkaline earth metals of Group II of the Periodic Table, e.g.,calcium, strontium, barium and in some cases magnesium. Conventionalacidic alkoxylation catalysts include, broadly, Lewis acid orFriedel-Crafts catalysts. Specific examples of these acid catalysts arethe fluorides, chlorides, and bromides of boron, antimony, tungsten,iron, nickel, zinc, tin, aluminum, titanium and molybdenum. The use ofcomplexes of such halides with, for example, alcohols, ethers,carboxylic acids, and amines has also been reported. Still otherexamples of known acidic alkoxylation catalysts are sulfuric andphosphoric acids; perchloric acid and the perchlorates of magnesium,calcium, manganese, nickel and zinc; certain metal oxalates, sulfates,phosphates, carboxylates and acetates, alkali metal fluoroborates., zinctitanate, and certain metal salts of benzene sulfonic acid.

Other art on the subject of alkoxylation includes U.S. Pat. No.4,727,199, which describes a process for reacting a liquid or solidalkylene oxide with a liquid or gaseous active hydrogen compound in thepresence of a catalytic amount of an anion-bound metal oxideheterogenous catalyst, wherein the anion is SO₄, BF₄, CO₃, BO₃, PO₄,SeO₄, MoO₄, B₄ O₇ or PF₆ and the metal oxide is an oxide of zirconium,nickel, aluminum, tin, calcium, magnesium, iron, titanium, thorium,hafnium, or rubidium. Still other prior art describes the use ofzeolitic materials as alkoxylation catalysts, while European patentapplication 0250168 and other art cited therein disclose lamellar claycatalysts.

Alkylene oxide addition reactions are known to produce a product mixtureof various alkoxylate molecules having different numbers of alkyleneoxide adducts (oxyalkylene adducts), e.g., having different values forthe adduct number n in formula III above. The adduct number is a factorwhich in many respects controls the properties of the alkoxylatemolecule, and efforts are made to tailor the average adduct number of aproduct and/or the distribution of adduct numbers within a product tothe product's intended service. In certain preferred embodiments, thepresent invention provides a process characterized by enhancedselectivity for the preparation of alkoxylate mixtures in which arelatively large proportion of the alkoxylate molecules have a number(n) of alkylene oxide adducts that is within a relatively narrow rangeof values.

It is known in the art that alcohol alkoxylate products having a narrowrange alkylene oxide adduct distribution are preferred for use incertain detergent formulations (Great Britain Pat. No. 1,462,134.,Derwent Publications Research Disclosure number 194,010). Narrow-rangealcohol alkoxylates are also known to be particularly valuable aschemical intermediates in the synthesis of certain carboxyalkylatedalkyl polyethers (U.S. Pat. No. 4,098,818) and of certain alkyl ethersulfates (Great Britain Pat. No. 1,553,561). Conventional commercialalkoxylate preparation, which has in large part been limited to the useof basic catalysts, particularly the metals sodium and potassium andtheir oxides and hydroxides, yields only a relatively broad distributionrange product. Conventional acid-catalyzed alkoxylation reactions havelong been known to produce a more narrow range product than thatobtained with the alkali metal catalysts. However, acid catalysts havesubstantial disadvantages in several other respects. For instance, theacids are often unstable with limited life and effectiveness ascatalysts in the alkoxylation mixture. Both the acid catalyststhemselves and their decomposition products catalyze side reactionsproducing relatively large amounts of polyalkylene glycols, and alsoreact directly with the components of the alkoxylation mixture to yieldundesirable, and often unacceptable, by-products such as organicderivatives of the acids.

Also of substantial importance in alkoxylation processes is the abilityof the process to minimize the quantity of unreacted (or residual)active hydrogen reactant remaining in the final product. A high level ofresidual reactant either represents a loss of valuable reactant, orrequires that further processing of the product be carried out torecover the reactant. Moreover, the presence of the unreacted materialis often a disadvantage from the standpoint of product quality andenvironmental concerns. For instance, residual alkanol in a detergentalcohol ethoxylate product contributes to volatile organic emissionsduring spray drying of detergent formulations.

It has recently been reported in the art that, in addition toconventional acidic catalysts, a number of other substances have beenfound to function as catalysts or in co-catalyst combinations which arecapable of producing relatively narrow distributions for the oxyalkyleneadducts of higher alkanols and other active hydrogen containingcompounds. For instance, it has recently been disclosed (U.S. Pat. Nos.4,306,093 and and 4,239,917, and published European patent applicationNos. 0026544, 0026546, 0026547) that certain compounds of barium,strontium, and calcium promote narrow-range alkoxylation products. U.S.Pat. Nos. 4,210,764 and 4,223,164 describe the use of cresylic acids topromote alkoxylation catalyzed by barium and strontium compounds. U.S.Pat. No. 4,302,613 discloses that a more peaked reaction product can beobtained by combining barium and strontium alkoxylation catalysts withco-catalysts such as calcium oxide, calcium carbide, calcium hydroxide,magnesium metal, magnesium hydroxide, zinc oxide and aluminum metal.U.S. Pat. No. 4,453,023 describes a process for preparing alkoxylateshaving a narrower molecular weight distribution which employs a catalystcomprising a barium compound and a promoter selected from the classconsisting of superphosphoric acid, phosphoric acid, diphosphoric acid,triphosphoric acid, phosphorous acid, dihydrogen phosphate compounds,oxides of phosphorous, carbon dioxide, and oxalic acid. U.S. Pat. No.4,453,022 describes a similar process wherein the catalyst comprises acalcium or strontium compound and a promoter selected from the classconsisting of superphosphoric acid, phosphoric acid, diphosphoric acid,triphosphoric acid, phosphorous acid, dihydrogen phosphate compounds,oxides of phosphorus, sulfuric acid, bisulfate compounds, carbonic acid,bicarbonate compounds, carbon dioxide, oxalic acid and oxalic acidsalts, sulfur trioxide, sulfur dioxide, and sulfurous acid. PublishedPCT application WO 85/00365 discloses other activated calcium containingalkoxylation catalysts capable of producing narrow range alkoxylationproducts. U.S. Pat. No. 4,375,564 reports that a narrow range productresults from alkoxylation reactions catalyzed by a magnesium compound incombination with a compound of one of the elements aluminum, boron,zinc, titanium, silicon, molybdenum, vanadium, gallium, germanium,yttrium, zirconium, niobium, cadmium, indium, tin, antimony, tungsten,hafnium, tantalum, thallium, lead and bismuth. U.S. Pat. No. 4,483,941discloses catalysts for alkoxylation reactions which comprise either BF₃or SiF₄ in combination with an alkyl or alkoxide compound of aluminum,gallium, indium, thallium, titanium, zirconium, and hafnium. U.S. Pat.No. 4,456,697 describes an alkoxylation catalyst which comprises amixture of HF and one or more metal alkoxides. Japanese patentspecification 52051307 to Tokuyama Soda KK discloses the selectivepreparation of mono- rather than di- or tri-alkylene glycol esters fromalkYlene oxide and alcohol using solid acid catalysts such as silica,alumina, titania, vanadium pentoxide, antimony pentoxide, titanylsulfate, tungstic acid, phosphotungstic acid, and silver perchlorite.

Recently issued U.S. Pat. No. 4,721,816 claims a process for preparingnarrow range distribution alkoxylates, wherein the catalyst is acombination of one or more sulfur-containing acids with one or morealuminum alcoholate or phenolate compounds. U.S. Pat. No. 4,721,817claims a similar process wherein the combination contains one or morephosphorus-containing acids.

U.S. Pat. Nos. 4,665,236 and 4,689,435 describe a process for thealkoxylation of active hydrogen reactants using certain bimetallic oxocatalysts. With regard to the use in this invention of catalystscomprising one or more silicate salts of the element lanthanum, thecatalysts described in U.S. Pat. No. 4,665,236 include compounds inwhich one of the metal species in the bimetallic molecule is lanthanum,and European application 0250168 discloses lamellar clay catalysts whichhave been ion exchanged with lanthanum and other rare earth elements.

SUMMARY OF THE INVENTION

It has now been found that lanthanum silicates and/or lanthanummetasilicates are effective catalysts for the addition reaction ofalkylene oxides with organic compounds having active hydrogen atoms. Ithas further been found that, in certain preferred embodiments, analkoxylation reaction catalyzed by a lanthanum silicate provides analkoxylate product, particularly an alkanol ethoxylate product, ofexceptionally narrow-range alkylene oxide adduct distribution.

The present invention is particularly directed to a process for thepreparation of alkoxylates of active hydrogen containing organiccompounds which comprises contacting an alkYlene oxide reactantcomprising one or more vicinal alkylene oxides with an active hydrogenreactant comprising one or more organic compounds (e.g., alcohols,phenols, thiols, amines, polyols, carboxylic acids, etc.) having one ormore active hydrogen atoms, in the presence of a catalytically effectiveamount of lanthanum in combination with one or more metal-free anionsselected from the group consisting of silicate, metasilicate andmixtures thereof.

As used herein, the terms "silicate" and "metasilicate" refer to anionscontaining silica and oxygen and optionally, waters of hydration. It isunderstood that the silicates and metasilicates can have wide ranges ofstoichiometries.

In general terms, the catalyst for the process of the inventioncomprises one or more of the silicate or metasilicate salts of thelanthanum. In particularly preferred embodiments, the catalystadditionally contains hydroxide and/or phosphate.

The lanthanum silicate and/or metasilicate salts are present in thealkoxylation mixture in catalytically effective amounts in either (orboth) homogeneous or heterogeneous form(s), although heterogeneouscatalysts have been found to be preferred in certain embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention centers upon discoveries associated with the usein an alkoxylation process of a certain class of catalysts. Apart fromthe use of such catalysts, the process of the invention is, as a generalrule, suitably conducted using such reactants and practicing under suchprocessing procedures and reaction conditions as are well known to theart for alkoxylation reactions. Certain preferences may, however, beexpressed for particular reactants, procedures and conditions.

Thus, for instance, the invention is preferably applied to processesutilizing an alkYlene oxide (epoxide) reactant which comprises one ormore vicinal alkylene oxides, particularly the lower alkylene oxides andmore particularly those in the C₂ to C₄ range. In general, the alkyleneoxides are represented by the formula ##STR2## wherein each of the R¹,R², R³ and R⁴ moieties is individually selected from the groupconsisting of hydrogen and alkyl moieties. Reactants which compriseethylene oxide, propylene oxide, or mixtures of ethylene oxide andpropylene oxide are more preferred, particularly those which consistessentially of ethylene oxide and propylene oxide. Alkylene oxidereactants consisting essentially of ethylene oxide are considered mostpreferred from the standpoint of commercial opportunities for thepractice of alkoxylation processes, and also from the standpoint of thepreparation of products having narrow-range ethylene oxide adductdistributions.

Likewise, the active hydrogen reactants suitably utilized in the processof the invention include those known in the art for reaction withalkylene oxides and conversion to alkoxylate products. Suitable classesof active hydrogen reactants include (but are not necessarily limitedto) alcohols, phenols, thiols (mercaptans), amines, polyols, carboxylicacids, and mixtures thereof. Preference generally exists for use ofhydroxyl-containing reactants. More preferably, the active hydrogencontaining reactant consists essentially of one or more active hydrogencontaining compounds selected from the group consisting of alkanols,alkyl polyols and phenols (including alkyl-substituted phenols).

Among the suitable carboxylic acids, particular mention may be made ofthe mono- and dicarboxylic acids, both aliphatic (saturated andunsaturated) and aromatic. Specific examples include acetic acid,propionic acid, butyric acid, valeric acid, caproic acid, lauric acid,myristic acid, palmitic acid, steric acid, oleic acid, rosin acids, talloil acids, terephthalic acid, benzoic acid, phenylacetic acid, toluicacid, acrylic acid, methacrylic acid, crotonic acid, maleic acid, andthe like.

Among the suitable amines, particular mention may be made of primary,secondary and tertiary alkylamines and of alkylamines containing bothamino and hydroxyl groups, e.g., N,N-di(n-butyl)-ethanolamine andtripropanolamine.

Among the suitable thiols, particular mention may be made of primary,secondary and tertiary alkane thiols having from 1 to about 30 carbonatoms, particularly those having from about 8 to 20 carbon atoms.Specific examples of suitable tertiary thiols are those having a highlybranched carbon chain which are derived via hydrosulfurization of theproducts of the oligomerization of lower olefins, particularly thedimers, trimers, and tetramers and pentamers of propylene and thebutylenes. Secondary thiols are exemplified by the lower alkane thiols,such as 2-propanethiol, 2-butanethiol, and 3-pentanethiols, as well asby the products of the hydrosulfurization of the substantially linearoligomers of ethylene as are produced by the Oxo process. Representativebut not limiting examples of thiols derived from ethylene oligomersinclude the linear carbon chain products, such as 2-decanethiol,3-decanethiol, 4-decanethiol, 5-decanethiol, 3-dodecanethiol,5-dodecanethiol, 2-hexadecanethiol, 5-hexadecanethiol, and8-octadencanethiol, and the branched carbon chain products, such as2-methyl-4-tridecanethiol. Primary thiols are typically prepared fromterminal olefins by hydrosulfurization under free-radical conditions andinclude, for example, 1-butanethiol, 1-hexanethiol, 1-dodecanethiol,1-tetradecanethiol and 2-methyl-1-tridecanethiol.

Among the polyols, particular mention may be made of those having from 2to about 6 hydroxyl groups. Specific examples include the alkyleneglycols such as ethylene glycol, propylene glycol, hexylene glycol, anddecylene glycol, the polyalkylene glycol ethers, such as diethyleneglycol, triethylene glycol, propylene glycol, dipropylene glycol,tripropylene glycol, glycerine, sorbitol, and the like.

The alcohols (both mono- and poly-hydroxy) and the phenols (includingalkyl-substituted phenols) are preferred classes of active hydrogenreactants for purposes of the invention. Among the phenols, particularmention may be made of phenol and of alkyl-substituted phenols whereineach alkyl substituent has from one to about 30 (preferably from one toabout 20) carbon atoms, for example, p-methylphenol, p-ethylphenol,p-hexylphenol, nonylphenol, p-decylphenol, didecyl phenol and the like.

Acyclic aliphatic mono-hydric alcohols (alkanols) form a most preferredclass of reactants, particularly the primary alkanols, althoughsecondary and tertiary alkanols are also very suitably utilized in theprocess of the invention. Preference can also be expressed, for reasonof both process performance and commercial value of the product, foralkanols having from one to about 30 carbon atoms, with C₆ to C₂₄alkanols considered more preferred and C₈ to C₂₀ alkanols consideredmost preferred. As a general rule, the alkanols may be of branched orstraight chain structure, although preference further exists for alkanolreactants in which greater than about 50 percent, more preferablygreater than about 60 percent, and most preferably greater than about 70percent of the molecules are of linear (straight-chain) carbonstructure.

The general suitability of such alkanols as reactants in alkoxylationreactions is well recognized in the art. Commercially available mixturesof primary mono-hydric alkanols prepared via the oligomerization ofethylene and the hydroformylation or oxidation and hydrolysis of theresulting higher olefins are particularly preferred. Examples ofcommercially available alkanol mixtures include the NEODOL Alcohols,trademark of and sold by Shell Chemical Company, including mixtures ofC₉, C₁₀ and C₁₁ alkanols (NEODOL 91 Alcohol), mixtures of C₁₂ and C₁₃alkanols (NEODOL 23 Alcohol), mixtures of C₁₂, C₁₃, C₁₄, and C₁₅alkanols (NEODOL 25 Alcohol), and mixtures of C₁₄ and C₁₅ alkanols(NEODOL 45 Alcohol); the ALFOL Alcohols, trademark of and sold by VistaChemical Company, including mixtures of C₁₀ and C₁₂ alkanols (ALFOL1012), mixtures of C₁₂ and C₁₄ alkanols (ALFOL 1214), mixtures of C₁₆and C₁₈ alkanols (ALFOL 1618), and mixtures of C₁₆, C₁₈ and C.sub. 20alkanols (ALFOL 1620); the EPAL Alcohols, trademark of and sold by EthylChemical Company, including mixtures of C₁₀ and C₁₂ alkanols (EPAL1012), mixtures of C₁₂ and C₁₄ alkanols (EPAL 1214), and mixtures ofC₁₄, C₁₆, and C₁₈ alkanols (EPAL 1418); and the TERGITOL-L Alcohols,trademark of and sold by Union Carbide Corporation, including mixturesof C₁₂, C₁₃, C₁₄, and C₁₅ alkanols (TERGITOL-L 125). Also very suitableare the commercially available alkanols prepared by the reduction ofnaturally occurring fatty esters, for example, the CO and TA products ofProcter and Gamble Company and the TA alcohols of Ashland Oil Company.

Among the polyols, particular mention may be made of those having from 2to about 6 hydroxyl groups and 2 or more, preferably 2 to 30 carbonatoms. Specific examples include the alkylene glycols such as ethyleneglycol, propylene glycol, hexylene glycol, and decylene glycol, thepolyalkylene glycol ethers, such as diethylene glycol, triethyleneglycol, propylene glycol, dipropylene glycol, tripropylene glycol,glycerine, sorbitol, and the like. Higher oligomers and polymers of thepolyols are also very suitable.

The active hydrogen containing reactant is also very suitably thealkoxylate product of a previous alkoxylation of an active hydrogencontaining compound.

Further examples of both specific alkylene oxide reactants and specificactive hydrogen containing reactants suitable for use in this inventionare recited in the aforementioned U.S. Patents, the relevant disclosuresof which are incorporated herein by this reference.

The alkylene oxide reactant and the active hydrogen reactant arenecessarily contacted in the presence of compounds comprising lanthanumsilicate, lanthanum metasilicate and mixtures thereof.

In addition to a catalytically effective amount of the lanthanumsilicate and/or metasilicate, the catalyst for the process of theinvention may also suitably contain other substances, including boththose which may be introduced into the process as impurities in thesilicate salt catalyst as well as those which may be added to promote ormodify catalyst activity. The lanthanum silicate and/or lanthanummetasilicate may contain hydroxide and/or phosphate thus formingphosphate silicates, phosphate metasilicates, hydroxysilicates,hydroxymetasilicates, hydroxyphosphate silicates and hydroxyphosphatemetasilicates.

The one or more of the silicate/metasilicate salts of lanthanum arepresent in the reaction mixture in a catalytically effective amount,i.e., an amount sufficient to promote the alkoxylation reaction orinfluence the alkylene oxide adduct distribution of the product.Although a specific quantity of catalyst is not critical to theinvention, preference may be expressed for use of the catalyst in amountof at least about 0.01 percent by weight, while an amount between about0.02 percent by weight and about 5.0 percent by weight is consideredmore preferred and an amount between about 0.1 percent by weight andabout 2.0 percent by weight is considered most preferred for typicalembodiments. These percentages are in terms of the weight of lanthanumions in the process mixture relative to the weight of active hydrogencontaining compounds in that mixture. Substantially greater quantitiesof catalyst, e.g., up to about 10 percent by weight or more, are alsovery suitable. As a rule, the higher the desired average alkylene oxideadduct number of the alkoxylate product and the higher the desired rateof reaction, the greater the required quantity of catalyst.

The silicate/metasilicate catalysts in the instant invention cansuitably be prepared in any conventional manner such as, for example, bya metathesis reaction of a lanthanum salt such as lanthanum chloride anda silicate salt such as sodium silicate and/or a metasilicate salt suchas sodium metasilicate. The catalysts are typically prepared byco-precipitation at a temperature of 25° C. In addition, hydroxideand/or phosphate can be added to the silicate and/or metasilicate. In apreferred embodiment, the catalyst is a silicate phosphate or ametasilicate phosphate.

In a particularly important embodiment, the invention is a process whichcomprises contacting and reacting an alkylene oxide reactant(particularly a reactant comprising ethylene oxide, propylene oxide, ora mixture of propylene oxide and ethylene oxide) with an active hydrogencontaining reactant (particularly an alcohol, polyol, or other hydroxylcontaining compound), in the presence of a catalyst which comprises oneor more lanthanum compounds, at least one silicate or metasilicate anionand optionally, a phosphate and/or a hydroxide ion. In a most preferredembodiment, ethylene oxide is contacted with a C₁ to C₃₀ primary alkanolin the presence of a catalytically effective amount of such a compound.

In terms of processing procedures, the alkoxylation reaction in theinvention may be conducted in a generally conventional manner. Forexample, the catalyst may initially be mixed with liquid active hydrogenreactant. The mixture of catalyst and liquid reactant is contacted,preferably under agitation, with alkylene oxide reactant, which istypically introduced in gaseous form, at least for the lower alkyleneoxides. The order in which the reactants and catalyst are contacted hasnot been found to be critical to the invention.

While these procedures describe a batch mode of operation, the inventionis equally applicable to a continuous process.

Overall, the two reactants are utilized in quantities which arepredetermined to yield an alkoxylate product of the desired mean oraverage adduct number. The average adduct number of the product is notcritical to this process. Such products commonly have an average adductnumber in the range from less than one to about 30 or greater.

In general terms, suitable and preferred process temperatures andpressures for purposes of this invention are the same as in conventionalalkoxylation reactions between the same reactants, employingconventional catalysts. A temperature of at least about 90° C.,particularly at least about 120° C. and most particularly at least about130° C., is typically preferred from the standpoint of the rate ofreaction, while a temperature less than about 250° C., particularly lessthan about 210° C., and most particularly less than about 190° C., istypically desirable to minimize degradation of the product. As is knownin the art, the process temperature can be optimized for givenreactants, taking such factors into account.

Super-atmospheric pressures, e.g., pressures between about 10 and 150psig, are preferred, with pressure being sufficient to maintain theactive hydrogen reactant substantially in the liquid state.

When the active hydrogen reactant is a liquid and the alkylene oxidereactant is a vapor, alkoxylation is then suitably conducted byintroducing alkylene oxide into a pressure reactor containing the liquidactive hydrogen reactant and the catalyst. For considerations of processsafety, the partial pressure of a lower alkYlene oxide reactant ispreferably limited, for instance, to less than about 60 psia, and/or thereactant is preferably diluted with an inert gas such as nitrogen, forinstance, to a vapor phase concentration of about 50 percent or less.The reaction can, however, be safely accomplished at greater alkyleneoxide concentration, greater total pressure and greater partial pressureof alkylene oxide if suitable precautions, known to the art, are takento manage the risks of explosion. A total pressure of between about 40and 110 psig, with an alktlene oxide partial pressure between about 15and 60 psig, is particularly preferred, while a total pressure ofbetween about 50 and 90 psig, with an alkylene oxide partial pressurebetween about 20 and 50 psig, is considered more preferred.

The time required to complete a process according to the invention isdependent both upon the degree of alkoxylation that is desired (i.e.,upon the average alkylene oxide adduct number of the product) as well asupon the rate of the alkoxylation reaction (which is, in turn dependentupon temperature, catalyst quantity and nature of the reactants). Atypical reaction time for preferred embodiments is in the range from 1to 24 hours.

After the ethoxylation reaction has been completed, the product ispreferably cooled. If desired, catalyst can be removed from the finalproduct, although catalyst removal is not necessary to the process ofthe invention. Catalyst residues may be removed, for example, byfiltration, precipitation, extraction, or the like.

The following Examples are provided to further illustrate certainspecific aspects of the invention but are not intended to limit itsbroader scope.

EXAMPLE 1

A lanthanum silicate catalyst was prepared by the following procedure. Afirst solution was prepared by dissolving 15.0 grams of lanthanumchloride (LaCl₃ ·7H₂ O: 40 mmoles) in 50 milliliters of deionized water.A second solution was prepared by dissolving 5.52 grams of sodiumsilicate (Na₄ SiO₄ : 30 mmoles) in 50 milliliters of water. The twosolutions were then coprecipitated in a vessel containing 200milliliters of water. A white precipitate formed immediately. The slurrywas stirred for 30 minutes at room temperature and then filtered andwashed with water. The solid formed was dried in a vacuum oven at 120°C. The material prepared was amorphous by x-ray diffraction.

An alkoxylation process in accordance with the invention was conductedunder the following procedures. The alkylene oxide reactant for thisprocess embodiment consisted of ethylene oxide and the active hydrogencontaining reactant consisted of NEODOL 23 Alcohol (NEODOL is atrademark of Shell Chemical Company) characterized as a mixture ofprimary, 80% linear (20% branched), alkanols having twelve and thirteencarbon atoms (about 40% by mol C₁₂ and 60% by mol C₁₃).

Initially, 2.0 grams of the powder prepared as described above was addedto 110 grams of NEODOL 23 Alcohol, and the mixture was heated in a 500milliliter autoclave to 140° C. under nitrogen sparge to drive offwater. A mixture of nitrogen and ethylene oxide was then introduced intothe reactor to a total pressure of 75 psia (45 psia nitrogen and 30 psiaethylene oxide). Alkoxylation (ethoxylation) commenced immediately.Additional ethylene oxide was supplied on demand to maintain anessentially constant 75 psia pressure. Temperature was maintained at140° C. A total of 90 grams of ethylene oxide was taken up over a periodof 4.8 hours. The reactor was maintained for an additional 1 hour toconsume unreacted ethylene oxide in the system.

The product was analyzed by GC-LC techniques and found to have a meanaverage adduct number of 3.2. The ethylene oxide adduct distribution ofthe product is presented in the following table. The only observedby-products were polyethylene glycols (PEG).

    ______________________________________                                        ETHOXYLATE DISTRIBUTION                                                       Adduct Number      Concentration                                              ______________________________________                                        0        (Residual Alcohol)                                                                          8.4% wt                                                1                      5.4                                                    2                      11.4                                                   3                      20.6                                                   4                      21.4                                                   5                      14.4                                                   6                      7.4                                                    7                      3.8                                                    8                      2.2                                                    9                      1.3                                                    10                     0.9                                                    11                     0.6                                                    12                     0.5                                                    13                     0.4                                                    14                     0.3                                                    15                     0.3                                                    ______________________________________                                    

EXAMPLE 2

A lanthanum hydroxymetasilicate catalyst was prepared according to thefollowing procedure. A first solution was prepared by dissolving 15.0grams of lanthanum chloride (LaCl₃ ·7H₂ O: 40 mmoles) in 50 millilitersof deionized water. A second solution was prepared by dissolving 8.49grams of sodium metasilicate (Na₂ SiO₃ ·5H₂ O: 40 mmoles) in 50milliliters of water. A third solution was prepared by dissolving 1.6grams of sodium hydroxide (NaOH: 40 mmoles) in 50 milliliters of water.The three solutions were then simultaneously added to a vesselcontaining 200 milliliters of water. The white gelatinous precipitateformed was stirred at room temperature for 30 minutes. The slurry wasfiltered and the solids washed with 200 milliliters of deionized water.The solid formed was dried in a vacuum oven at 120° C.

Two grams of this powder was added to 110 grams of the NEODOL 23 Alcoholin a 500 milliliter autoclave, and the temperature of the mixture wasramped to 140° C. under nitrogen sparge to drive off water. The alcoholwas ethoxylated at 140° C. and at a pressure of 75 psia (30 psiaethylene oxide and 45 psia nitrogen). A total of 188 grams of ethyleneoxide was consumed over a period of 6 hours, yielding a product having amean average adduct number of 6.7. The adduct distribution of thisproduct is presented in the following table.

    ______________________________________                                        ETHOXYLATE DISTRIBUTION                                                       Adduct Number      Concentration                                              ______________________________________                                        0        (Residual Alcohol)                                                                          2.0% wt                                                1                      0.7                                                    2                      0.5                                                    3                      1.2                                                    4                      3.5                                                    5                      9.7                                                    6                      17.9                                                   7                      20.9                                                   8                      17.3                                                   9                      11.1                                                   10                     6.3                                                    11                     3.4                                                    12                     1.9                                                    13                     1.1                                                    14                     0.7                                                    15                     0.5                                                    ______________________________________                                    

EXAMPLE 3

A lanthanum phosphate silicate catalyst was prepared under the followingprocedure. A first solution was prepared by dissolving 15.0 grams oflanthanum chloride (LaCl₃ ·7H₂ O: 40 mmoles) in 100 milliliters ofdeionized water. A second solution was prepared by dissolving 1.86 gramsof sodium silicate (Na₄ SiO₄ : 10 mmoles) in 100 milliliters of water. Athird solution was prepared by dissolving 10.2 grams sodium phosphate(Na₃ PO₄ ·12H₂ O: 27 mmoles) in 100 milliliters of water. The threesolutions were then simultaneously added during a 10 minute period to avessel containing 200 milliliters of deionized water. The thick whitegelatinous precipitate formed was stirred at room temperature for 30minutes. The slurry was filtered and the solids washed with 600milliliters of deionized water. The solid formed was dried in a vacuumoven at 120° C.

One gram of this powder was added to 110 grams of NEODOL 23 Alcohol. Anethoxylation reaction was then carried out according to the proceduresdescribed in Example 2. A total of 180 grams of ethylene oxide wasconsumed over a 4 hour period at a reaction temperature of 140° C. Theproduct had a mean average adduct number of 6.6. The adduct distributionof this product is presented in the following table.

    ______________________________________                                        ETHOXYLATE DISTRIBUTION                                                       Adduct Number      Concentration                                              ______________________________________                                        0        (Residual Alcohol)                                                                          1.9% wt                                                1                      0.4                                                    2                      0.6                                                    3                      1.5                                                    4                      4.2                                                    5                      10.9                                                   6                      18.6                                                   7                      20.8                                                   8                      16.5                                                   9                      10.4                                                   10                     5.8                                                    11                     3.1                                                    12                     1.8                                                    13                     1.1                                                    14                     0.7                                                    15                     0.5                                                    ______________________________________                                    

EXAMPLE 4

A mixed lanthanum phosphate metasilicate catalyst was prepared accordingto the following procedure. A first solution was prepared by dissolving15 grams of lanthanum chloride (LaCl₃ ·7H₂ O: 40 mmoles) in 100milliliters of deionized water. A second solution was prepared bydissolving 2.86 grams of sodium metasilicate (Na₂ SiO₃ ·5H₂ O: 13.5mmoles) in 100 milliliters of water. A third solution was prepared bydissolving 11.9 grams sodium phosphate (Na₃ PO₄ ·12H₂ O: 31.4 mmoles) in100 milliliters of water. The three solutions were then simultaneouslyadded during a 10 minute period to a vessel containing 200 millilitersof water. The thick white gelatinous precipitate formed was stirred atroom temperature for 30 minutes. The slurry was filtered and the solidswashed with 600 milliliters of deionized water. The solid formed wasdried in a vacuum oven at 120° C.

One gram of this powder was added to 110 grams of NEODOL 23 Alcohol. Anethoxylation reaction was then carried out according to the proceduresdescribed in Example 2. A total of 180 grams of ethylene oxide wasconsumed in 3 hours. The average adduct number of the product was 6.5The adduct distribution of the product is presented in the followingtable.

    ______________________________________                                        ETHOXYLATE DISTRIBUTION                                                       Adduct Number      Concentration                                              ______________________________________                                        0        (Residual Alcohol)                                                                          1.9% wt                                                1                      0.5                                                    2                      0.9                                                    3                      1.5                                                    4                      4.7                                                    5                      12.6                                                   6                      20.5                                                   7                      20.7                                                   8                      14.8                                                   9                      8.5                                                    10                     4.7                                                    11                     2.7                                                    12                     1.7                                                    13                     1.1                                                    14                     0.8                                                    15                     0.7                                                    ______________________________________                                    

What is claimed is:
 1. A process for the preparation of alkylene oxideadducts of active hydrogen containing organic compounds, which comprisescontacting and reacting an alkylene oxide reactant comprising one ormore vicinal alkylene oxides with an active hydrogen containing reactantcomprising one or more active hydrogen containing organic compounds, inthe presence of a catalytically effective amount of one or morelanthanum compounds comprising lanthanum silicate, lanthanummetasilicate and mixtures thereof.
 2. The process of claim 1 wherein thelanthanum compounds additionally comprise a compound selected from thegroup consisting of hydroxide, phosphate and mixtures thereof.
 3. Theprocess of claim 1 wherein said lanthanum compound comprises lanthanumsilicate.
 4. The process of claim 3 wherein said lanthanum silicateadditionally comprises a compound selected from the group consisting ofhydroxide, phosphate and mixtures thereof.
 5. The process of claim 1wherein said lanthanum compound is of lanthanum metasilicate.
 6. Theprocess of claim 5 wherein said lanthanum metasilicate additionallycomprises a compound selected from the group consisting of hydroxide,phosphate and mixtures thereof.
 7. The process of claim 1 wherein thealkylene oxide reactant consists essentially of one or more alkyleneoxides selected from the group consisting of ethylene oxide andpropylene oxide.
 8. The process of claim 7 wherein the active hydrogencontaining reactant consists essentially of one or more compoundsselected from the group consisting of alkanols, phenols and polyols. 9.The process of claim 8 wherein the active hydrogen containing reactantconsists essentially of one or more active hydrogen containing compoundsselected from the group consisting of alkanols having from one to about30 carbon atoms and alkyl-substituted phenols wherein each alkylsubstituent has from one to about 30 carbon atoms.
 10. The process ofclaim 9 wherein the active hydrogen containing reactant consistsessentially of one or more C₁ -C₃₀ primary mono-hydric alkanols.
 11. Theprocess of claim 10 wherein the active hydrogen containing reactantconsists essentially of primary mono-hydric alkanols having carbonnumbers in the range from 6 to 24, inclusive, and the alkylene oxidereactant consists essentially of ethylene oxide.
 12. The process ofclaim 11 wherein the active hydrogen containing reactant consistsessentially of primary mono-hydric alkanols having carbon numbers in therange from 8 to 20, inclusive.
 13. The process of claim 12 whereingreater than about 50% of the molecules of the primary mono-hydricalkanols are of linear carbon structure.
 14. The process of claim 13wherein greater than about 70% of the molecules are of linear carbonstructure.
 15. A process for the preparation of alkylene oxide adductsof active hydrogen containing organic compounds, which comprisescontacting and reacting an alkylene oxide selected from the groupconsisting of ethylene oxide and propylene oxide, with an activehydrogen containing reactant selected from the group consisting ofalkanols, phenols and polyols, in the presence of a catalyticallyeffective amount of lanthanum silicate.
 16. The process of claim 15wherein said lanthanum silicate additionally comprises a compoundselected from the group consisting of hydroxide, phosphate and mixturesthereof.
 17. The process of claim 15 wherein the active hydrogencontaining reactant consists essentially of one or more active hydrogencontaining compounds selected from the group consisting of alkanolshaving from one to about 30 carbon atoms and alkyl-substituted phenolswherein each alkyl substituent has from one to about 30 carbon atoms.18. The process of claim 17 wherein the active hydrogen containingreactant consists essentially of one or more C₁ -C₃₀ primary mono-hydricalkanols.
 19. The process of claim 18 wherein the active hydrogencontaining reactant consists essentially of primary mono-hydric alkanolshaving carbon numbers in the range from 6 to 24, inclusive, and thealkylene oxide reactant consists essentially of ethylene oxide.
 20. Theprocess of claim 19 wherein the active hydrogen containing reactantconsists essentially of primary mono-hydric alkanols having carbonnumbers in the range from 8 to 20, inclusive.
 21. The process of claim20 wherein greater than about 50% of the molecules of the primarymono-hydric alkanols are of linear carbon structure.
 22. The process ofclaim 21 wherein greater than about 70% of the molecules are of linearcarbon structure.
 23. A process for the preparation of alkYlene oxideadducts of active hydrogen containing organic compounds, which comprisescontacting and reacting an alkylene oxide selected from the groupconsisting of ethylene oxide and propylene oxide, with an activehydrogen reactant selected from the group consisting of alkanols,phenols and polyols, in the presence of a catalytically effective amountof lanthanum metasilicate.
 24. The process of claim 23 wherein saidlanthanum metasilicate additionally comprises a compound selected fromthe group consisting of hydroxide, phosphate and mixtures thereof. 25.The process of claim 23 wherein the active hydrogen containing reactantconsists essentially of one or more active hydrogen containing compoundsselected from the group consisting of alkanols having from one to about30 carbon atoms and alkyl-substituted phenols wherein each alkylsubstituent has from one to about 30 carbon atoms.
 26. The process ofclaim 25 wherein the active hydrogen containing reactant consistsessentially of one or more C₁ -C₃₀ primary mono-hydric alkanols.
 27. Theprocess of claim 26 wherein the active hydrogen containing reactantconsists essentially of primary mono-hydric alkanols having carbonnumbers in the range from 6 to 24, inclusive, and the alkylene oxidereactant consists essentially of ethylene oxide.
 28. The process ofclaim 27 wherein the active hydrogen containing reactant consistsessentially of primary mono-hydric alkanols having carbon numbers in therange from 8 to 20, inclusive.
 29. The process of claim 28 whereingreater than about 50% of the molecules of the primary mono-hydricalkanols are of linear carbon structure.
 30. The process of claim 29wherein greater than about 70% of the molecules are of linear carbonstructure.